Li2O-Al2O3-SiO2 based crystallized glass and production method for the same

ABSTRACT

An object of the present invention is to provide a Li 2 O—Al 2 O 3 —SiO 2  based crystallized glass with excellent bubble quality even without using As 2 O 3  or Sb 2 O 3  as a fining agent and a method for producing the same. The Li 2 O—Al 2 O 3 —SiO 2  based crystallized glass of the present invention is a Li 2 O—Al 2 O 3 —SiO 2  based crystallized glass which does not substantially comprise As 2 O 3  and Sb 2 O 3  and comprises at least one of Cl, CeO 2  and SnO 2 , and has a S content of not more than 10 ppm in terms of SO 3 .

TECHNICAL FIELD

The present invention relates to a Li₂O—Al₂O₃—SiO₂ based crystallizedglass and a production method the same.

BACKGROUND ART

A Li₂O—Al₂O₃—SiO₂ based crystallized glass contains, as a main crystal,a β-quartz solid solution (Li₂O.Al₂O₃.nSiO₂ [n ≧2]) or a β-spodumenesolid solution (Li₂O.Al₂O₃.nSiO₂ [n≧4]), and hence, it has suchcharacteristic that expansion is extremely low and that mechanicalstrength is high. Therefore, the Li₂O—Al₂O₃—SiO₂ based crystallizedglass has excellent thermal characteristics. In addition, since acrystal to be precipitated can be changed by changing a heat treatmentcondition in a crystallization step, both a transparent crystallizedglass in which a β-quartz solid solution precipitates and a white opaquecrystallized glass in which a β-spodumene solid solution precipitatescan be produced from a mother glass (crystallizable glass) of the samecomposition and used for different purposes according to an application.

Making use of such characteristics, the Li₂O—Al₂O₃—SiO₂ basedcrystallized glass previously has been used for various applications;such as front windows of oil stoves, wood stoves, and the like,substrates for high-technology products such as color filter substrates,image sensor substrates, substrates for top plates of electromagneticcookers, gas cookers, and the like, window glasses for fire-retardingdoors, base materials for reflecting mirrors to be used for projectorssuch as liquid crystal projectors, or light source lamps forillumination, setters for heat treatment of electronic components orplasma display panels, trays for microwave ovens, and electroniccomponents or precision machine components.

CITATION LIST Patent Document

Patent Document 1: JP-A-11-228180

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

In the case of producing a crystallized glass of this kind, in view ofthe fact that high-temperature viscosity of the glass is high, meltingat high temperatures exceeding 1,600° C. is required. In a glass withhigh viscosity, since bubbles are difficult to come to the surface, thebubbles in a glass melt are hardly removed. Then, As₂O₃ or Sb₂O₃ iswidely used as a fining agent. Now, there is a possibility that As₂O₃ orSb₂O₃ pollutes the environment at the time of glass producing process orwaste glass treatment or the like because of high toxicity thereof. As asolution, it is investigated to use SnO₂, CeO₂, Cl, or the like in placeof As₂O₃ or Sb₂O₃. For example, Patent Document 1 discloses aLi₂O—Al₂O₃—SiO₂ based crystallized glass using SnO₂ and Cl incombination as a fining agent.

However, there is a problem that even when SnO₂, CeO₂, Cl, or the likeis used as a fining agent in place of As₂O₃ or Sb₂O₃, a Li₂O—Al₂O₃—SiO₂based crystallized glass with excellent bubble quality is not alwaysobtainable. In particular, this tendency conspicuously occurs in thecase of producing the glass by a tank furnace for continuous production.If melting is performed using a crucible in a laboratory under astationary condition, a glass with good bubble quality is obtained,whereas in the case of applying to a tank furnace for continuousproduction, in many cases, a glass with good bubble quality is notobtained.

An object of the present invention is to provide a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass with excellent bubble quality even without usingAs₂O₃ or Sb₂O₃ as a fining agent and a method for producing the same.

Means for Solving the Problems

The present inventors made extensive and intensive investigations. As aresult, it has been found that a reason why a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass with excellent bubble quality is not stably obtainedby using a tank furnace for continuous production resides in reboil of S(sulfur) which is incorporated from a glass raw material.

Namely, S which is incorporated from a raw material or the like iscomprised as an impurity in a glass melt. In particular, there may bethe case where a lot of S is comprised as an impurity in Li₂CO₃ which isused as a Li₂O raw material. In addition, in the Li₂O—Al₂O₃—SiO₂ basedcrystallized glass, since the S solubility of the glass melt is low, Sis present in an instable state in the melt. Then, S is easily gasifieddue to a little change in the state (for example, oxidation-reduction,composition change, and temperature change). In comparison with the casewhere melting is performed in a stationary state as in a crucible testin a laboratory, in a tank furnace for continuous production, afluctuation in a charging condition of the raw material or a meltingcondition is large, and liquation of a refractory possibly occurs.Therefore, a state change of glass is liable to occur, and reboil due toS is liable to generate, so that it is difficult to obtain a productwith good bubble quality.

Even such a condition, in the case of using As₂O₃ or Sb₂O₃ as a finingagent, the S component in the glass melt is removed by a lot of a fininggas released from such a fining agent component, and the S concentrationin the melt remarkably decreases. In addition, if As₂O₃ or Sb₂O₃ ispresent in the melt, such a fining agent component oxidizes S, therebymaking S stably exist in a state of SO₄ ²⁻ in the glass melt. Therefore,SO₄ ²⁻ is hardly decomposed into SO₂ (gas)+O₂, so that it is possible tosuppress the gasification.

However, other fining agents than As₂O₃ or Sb₂O₃ are small in an effectfor removing S from the glass melt or an effect for making S stablyexist in a state of SO₄ ²⁻ in the glass melt. As a result, a so-calledreboil phenomenon in which S is bubbled as a SO₂ gas or the like fromthe glass melt is easy to occur. For example, if S is gasified in anamount of 1 ppm in terms of SO₃, it is calculated that several thousandto several ten thousand bubbles/kg are produced. Therefore, how toprevent reboil of S from occurring is very important in obtaining aLi₂O—Al₂O₃—SiO₂ based crystallized glass with less bubbles. Thisimportance is a phenomenon which is hardly recognized on a level of thelaboratory test using a crucible (in the case of using a platinumcrucible, since liquation of the crucible component hardly occurs,reboil due to S hardly occurs) and which has recognized first by theproduction in a tank furnace for continuous production under a conditionin which As₂O₃ or Sb₂O₃ is not comprised.

The present inventors have led to a proposal of the present invention onthe basis of the foregoing knowledge.

Specifically, the Li₂O—Al₂O₃—SiO₂ based crystallized glass of thepresent invention is characterized to be a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass, which does not substantially comprise As₂O₃ andSb₂O₃ and comprises at least one of Cl, CeO₂ and SnO₂, and has a Scontent of not more than 10 ppm in terms of SO₃. It is meant by theterms “not substantially comprise As₂O₃ and Sb₂O₃” as referred to in thepresent invention that the contents of these components are respectivelynot more than 100 ppm including impurities. The “Li₂O—Al₂O₃—SiO₂ basedcrystallized glass” means a crystallized glass comprising Li₂O, Al₂O₃and SiO₂ as essential components, and precipitating a n-quartz solidsolution and/or a β-spodumene solid solution as a main crystal. It ismeant by the terms “comprises at least one of Cl, CeO₂ and SnO₂” thatthese components are comprised solely or in combination and that acontent thereof is 0.02% by mass or more in terms of a combined content.The “S content” is a value determined by first dipping an analysissample in Na₂CO₃ by means of alkali fusion and filtering with a filterpaper, and subsequently stirring a filtrate thereof with an ion exchangeresin and again filtering, followed by measuring by means of ionchromatography.

In the present invention, it is preferable to comprise Cl in an amountof from 200 to 1,500 ppm. The content of Cl is a value determined bysubjecting a plate-shaped analysis sample to mirror polishing andmeasuring by a fluorescent X-ray analyzer.

By adopting the foregoing constitution, it is possible to obtain acrystallized glass with excellent clarity.

In the present invention, it is preferable that CeO₂ is notsubstantially comprised and SnO₂ is comprised in an amount of from 0.1to 0.5% by mass. It is meant by the terms “CeO₂ is not substantiallycomprised” as referred to in the present invention that the content ofCeO₂ is not more than 200 ppm including impurities.

In the case of using SnO₂ or CeO₂ as a fining agent, there is a concernthat the crystallized glass is colored. Though details of the mechanismin which the crystallized glass is colored are unclear, it may beconsidered that SnO₂ or CeO₂ reduces Fe that is an impurity at the stageof a heat treatment for crystallizing a glass. In particular, as toCeO₂, its influence is large. Then, by adopting the foregoingconstitution, it is possible to effectively prevent the coloration ofthe Li₂O—Al₂O₃—SiO₂ based crystallized glass from occurring. Inaddition, in the case of not using Cl, it becomes possible toeffectively avoid corrosion of forming equipment or the like.

In addition, by adding SnO₂, it is possible to decrease the amount ofdissolved SO₃ in the glass. It may be considered that this is caused dueto the fact that the S component in the glass melt is removed by afining gas released from the fining agent component. In addition, SnO₂has properties of releasing a fining gas at a higher temperature thanthat in As₂O₃ or Sb₂O₃ and hardly releases oxygen at the initial stageof melting where the temperature is low. Namely, even if SnO₂ is added,the atmosphere at the initial stage of melting hardly becomes oxidative.In view of the fact that when the atmosphere at the initial stage ofmelting becomes oxidative, S is easily dissolved into the glass melt, sothat the amount of remaining S is liable to become large, it may beconsidered that if SnO₂ is used, it is possible to effectively suppressthe dissolution of S at the initial stage of melting.

In the present invention, it is preferable to comprise from 50 to 80% ofSiO₂, from 12 to 30% of Al₂O₃, from 1 to 6% of Li₂O, from 0 to 5% ofMgO, from 0 to 10% of ZnO, from 0 to 8% of BaO, from 0 to 5% of Na₂O,from 0 to 10% of K₂O, from 0 to 8% of TiO₂, from 0 to 7% of ZrO₂, andfrom 0 to 7% of P₂O₅, in terms of a percentage by mass.

According to the foregoing constitution, it is possible to easily obtaina crystallized glass in which a β-quartz solid solution or a β-spodumenesolid solution precipitates as a main crystal and which is extremely lowin expansion and high in mechanical strength.

In the present invention, it is preferable to comprise from 20.5 to 30%by mass of Al₂O₃ and from 0.1 to 0.5% by mass of SnO₂ and satisfy arelation of 3.7≦Li₂O+0.741MgO+0.367ZnO≦4.5 in terms of a mass ratio.

Similar to CeO₂, there is a concern that SnO₂ causes coloration of thecrystallized glass. Then, in the case of using SnO₂ as a fining agent,by defining the composition to the foregoing range, it becomes possibleto reduce the coloration problem.

In addition, the Li₂O—Al₂O₃—SiO₂ based crystallized glass of the presentinvention is characterized to be a Li₂O—Al₂O₃—SiO₂ based crystallizedglass, which does not substantially comprise As₂O₃ and SB₂O₃, comprisesCl, and has a S content of not more than 10 ppm in terms of SO₃ and aβ-OH value of 0.2 /mm or more. It is meant by the terms “notsubstantially comprise As₂O₃ and Sb₂O₃” as referred to in the presentinvention that the contents of these components are respectively notmore than 100 ppm including impurities. The “Li₂O—Al₂O₃—SiO₂ basedcrystallized glass” means a crystallized glass comprising Li₂O, Al₂O₃and SiO₂ as essential components, and precipitating a β-quartz solidsolution and/or a β-spodumene solid solution as a main crystal. The “Scontent” is a value determined by first dipping an analysis sample inNa₂CO₃ by means of alkali fusion and filtering with a filter paper, andsubsequently stirring a filtrate thereof with an ion exchange resin andagain filtering, followed by measuring by means of ion chromatography.The “β-OH value” is a value calculated according to the followingequation.β-OH value (/mm)={log (T3850/T3500)}/t

T3850: Transmittance at 3850 cm⁻

T3500: Lowest transmittance in an absorption band in the vicinity of3500 cm⁻¹

t: Plate thickness of sample (mm)

In the present invention, it is preferable to comprise Cl in an amountof from 50 to 1,500 ppm. The content of Cl is a value determined bysubjecting a plate-shaped analysis sample to mirror polishing andmeasuring by a fluorescent X-ray analyzer.

By adopting the foregoing constitution, it is possible to obtain acrystallized glass with excellent clarity.

In the present invention, it is preferable that CeO₂ is notsubstantially comprised, and a content of SnO₂ is not more than 0.5% bymass. It is meant by the terms “CeO₂ is not substantially comprised” asreferred to in the present invention that the content of such componentis not more than 200 ppm including impurities.

In the case of using SnO₂ or CeO₂ as a fining agent, there is a concernthat the crystallized glass is colored. Though details of the mechanismin which the crystallized glass is colored are unclear, it may beconsidered that SnO₂ or CeO₂ reduces Fe that is an impurity at the stageof a heat treatment for crystallizing a glass. In particular, as toCeO₂, its influence is large. Then, by adopting the foregoingconstitution, it is possible to effectively prevent the coloration ofthe Li₂O—Al₂O₃—SiO₂ based crystallized glass from occurring.

Incidentally, by adding SnO₂, it is possible to decrease the amount ofdissolved SO₃ in the glass. It may be considered that this is caused dueto the fact that the S component in the glass melt is removed by afining gas released from the fining agent component. In addition, SnO₂has properties of releasing a fining gas at a higher temperature thanthat in As₂O₃ or Sb₂O₃ and hardly releases oxygen at the initial stageof melting where the temperature is low. Namely, even if SnO₂ is added,the atmosphere at the initial stage of melting hardly becomes oxidative.In view of the fact that when the atmosphere at the initial stage ofmelting becomes oxidative, S is easily dissolved into the glass melt, sothat the amount of remaining S is liable to become large, it may beconsidered that if SnO₂ is used, it is possible to effectively suppressthe dissolution of S at the initial stage of melting.

In the present invention, it is preferable to comprise from 50 to 80% ofSiO₂, from 12 to 30% of Al₂O₃, from 1 to 6% of Li₂O, from 0 to 5% ofMgO, from 0 to 10% of ZnO, from 0 to 8% of BaO, from 0 to 5% of Na₂O,from 0 to 10% of K₂O, from 0 to 8% of Ti0₂, from 0 to 7% of ZrO₂, andfrom 0 to 7% of P₂O₅, in terms of a percentage by mass.

According to the foregoing constitution, it is possible to easily obtaina crystallized glass in which a β-quartz solid solution or a β-spodumenesolid solution precipitates as a main crystal and which is extremely lowin expansion and high in mechanical strength.

In addition, the method for producing a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass of the present invention is characterized to be amethod for producing a Li₂O—Al₂O₃—SiO₂ based crystallized glass notsubstantially comprising As₂O₃ and Sb₂O₃, which comprises performingselection of a glass raw material and adjustment of a productioncondition so as to comprise at least one of Cl, CeO₂ and SnO₂, and havea S content of not more than 10 ppm in terms of SO₃. The “selection of aglass raw material” as referred to in the present invention meansselection of kind, grain size, purity, and the like of the glass rawmaterial. The “adjustment of a production condition” means adjustment ofmelting temperature, heating system, melting efficiency, and the like.The “Ce compound” means an oxide, a chloride, a hydroxide, a nitrate, orthe like comprising a Ce element. The “Sn compound” means an oxide, achloride, or the like comprising a Sn element.

In addition, the method for producing a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass of the present invention is characterized to be amethod for producing a Li₂O—Al₂O₃—SiO₂ based crystallized glass notsubstantially comprising As₂O₃ and Sb₂O₃, which comprises adding atleast one of a chloride, a Ce compound and a Sn compound to a glass rawmaterial batch, and controlling a content of S comprised in a glass rawmaterial to not more than 150 ppm in terms of SO₃. The “glass rawmaterial batch” as referred to in the present invention means a mixtureexcluding a chloride, a Ce compound, and a Sn compound in the glass rawmaterial. The “content of S comprised in a glass raw material” is one,in terms of SO₃, with respect to a value determined by dipping ananalysis sample in Na₂CO₃ by means of alkali fusion and filtering with afilter paper, and subsequently stirring a filtrate thereof with an ionexchange resin and again filtering, followed by measuring by means ofion chromatography.

In the present invention, it is preferable to add the chloride in anamount of from 0.04 to 0.3% by mass in terms of Cl based on 100% by massof the glass raw material batch.

By adopting the foregoing constitution, it becomes possible tosufficiently fine the glass.

In the present invention, it is preferable that the Ce compound is notadded and SnO₂ is comprised in an amount of from 0.1 to 0.5% by mass.

According to the foregoing constitution, it becomes easy to obtain acoloration-free Li₂O—Al₂O₃—SiO₂ based crystallized glass. In addition,in the case of not using Cl, it becomes possible to effectively avoidcorrosion of forming equipment or the like.

In the present invention, it is preferable to compound the glass rawmaterial batch so as to form a glass comprising from 50 to 80% of SiO₂,from 12 to 30% of Al₂O₃, from 1 to 6% of Li₂O, from 0 to 5% of MgO, from0 to 10% of ZnO, from 0 to 8% of BaO, from 0 to 5% of Na₂O, from 0 to10% of K₂O, from 0 to 8% of TiO₂, from 0 to 7% of ZrO₂, and from 0 to 7%of P₂O₅, in terms of a percentage by mass.

According to the foregoing constitution, it is possible to easilyproduce a crystallized glass in which a β-quartz solid solution or aβ-spodumene solid solution precipitates as a main crystal and which isextremely low in expansion and high in mechanical strength.

In the present invention, it is preferable to compound the glass rawmaterial batch so as to form a glass comprising from 20.5 to 30% by massof Al₂O₃ and from 0.1 to 0.5% by mass of SnO₂, and satisfying a relationof 3.7≦Li₂O+0.741 MgO+0.367ZnO≦4.5 in terms of a mass ratio.

According to the foregoing constitution, even in the case of using SnO₂as a fining agent, it becomes possible to reduce the coloration problem.In addition, by adding SnO₂, it is possible to decrease the dissolvedSO₃ amount in the glass.

In addition, the method for producing a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass of the present invention is characterized to be amethod for producing a Li₂O—Al₂O₃—SiO₂ based crystallized glass notsubstantially comprising As₂O₃ and Sb₂O₃, wherein a chloride is added tothe glass raw material batch, and the glass raw material and/or amelting condition is adjusted such that a content of S comprised in aglass raw material is controlled to not more than 150 ppm in terms ofSO₃, and such that a β-OH value of the obtained crystallized glass is0.2 /mm or more. The “glass raw material batch” as referred to hereinmeans a mixture excluding a fining agent such as a chloride in the glassraw material. In addition, the “content of S comprised in a glass rawmaterial” is one, in terms of SO₃, with respect to a value determined bydipping an analysis sample in Na₂CO₃ by means of alkali fusion andfiltering with a filter paper, and subsequently stirring a filtratethereof with an ion exchange resin and again filtering, followed bymeasuring by means of ion chromatography.

In the present invention, it is preferable to add the chloride in anamount of from 0.01 to 0.3% by mass in terms of Cl based on 100% by massof the glass raw material batch.

By adopting the foregoing constitution, it becomes possible tosufficiently fine the glass.

In the present invention, it is preferable that the Ce compound is notadded and the Sn compound is added as SnO₂ in an amount of not more than0.5% by mass.

According to the foregoing constitution, it becomes easy to obtain acoloration-free Li₂O—Al₂O₃—SiO₂ based crystallized glass.

In the present invention, it is preferable to compound the glass rawmaterial batch so as to foam a glass comprising from 50 to 80% of SiO₂,from 12 to 30% of Al₂O₃, from 1 to 6% of Li₂O, from 0 to 5% of MgO, from0 to 10% of ZnO, from 0 to 8% of BaO, from 0 to 5% of Na₂O, from 0 to10% of K₂O, from 0 to 8% of TiO₂, from 0 to 7% of ZrO₂, and from 0 to 7%of P₂O₅, in terms of a percentage by mass.

According to the foregoing constitution, it is possible to easilyproduce a crystallized glass in which a β-quartz solid solution or aβ-spodumene solid solution precipitates as a main crystal and which isextremely low in expansion and high in mechanical strength.

In the present invention, it is preferable to melt the glass in a tankfurnace.

According to the foregoing constitution, by applying to a tank furnacein which reboil of S is liable to occur, the effects of the presentinvention can be appropriately enjoyed.

Effects of the Invention

According to the present invention, in view of the fact that the contentof S comprised in the crystallized glass is a few, reboil of S is hardlygenerated. In consequence, even when As₂O₃ or Sb₂O₃ is not comprised, itis possible to stably obtain a crystallized glass with excellent bubblequality.

In addition, by adopting a constitution in which the contents of CeO₂and SnO₂ are controlled, it becomes easy to effectively suppress reboilwhile preventing coloration of the glass from occurring.

MODES FOR CARRYING OUT THE INVENTION

The Li₂O—Al₂O₃—SiO₂ based crystallized glass of the present invention isa glass which is preferable from the environmental standpoint because itdoes not substantially comprise As₂O₃ and Sb₂O₃. Then, Cl, CeO₂, and/orSnO₂ are comprised as a substitute fining agent for them.

The cause of bubbling generated in the case of not comprising As₂O₃ orSb₂O₃ resides in the S component comprised in the glass melt. Inconsequence, it is desirable that the content of the S component in theglass melt is small as far as possible. In the present invention, the Scontent, in terms of SO₃, is not more than 10 ppm, preferably less than10 ppm, not more than 8 ppm, less than 8 ppm, not more than 5 ppm, andespecially preferably less than 5 ppm.

As a method for reducing the S amount in the glass, it is desirable touse a raw material with a less S component. In addition thereto,however, there may be adopted measures such as (1) a method of addingSnO₂, (2) a method of increasing a water content in the glass melt inthe presence of Cl, (3) a method of adjusting a grain size of a SiO₂ rawmaterial, (4) a method of optimizing a batch melting temperature, and(5) a method of optimizing a melting efficiency. Incidentally, detailsof these measures are described later.

In addition, in the Li₂O—Al₂O₃—SiO₂ based crystallized glass of thepresent invention, at least one of Cl, CeO₂, and SnO₂ can be comprisedas the refining agent.

Cl has ability to sufficiently fine the glass and is preferable as thefining agent. In order to secure sufficient clarity, a content of Cl ispreferably from 200 to 1,500 ppm, more preferably from 400 to 1,000 ppm,and even more preferably from 500 to 900 ppm. When the content of Cl istoo small, the clarity is insufficient. On the other hand, when thecontent of Cl is too large, the volatilization amount as HCl is large,so that incidental equipment of the furnace is liable to be corroded.

Now, when Cl is used, there may be the case where incidental equipmentof the furnace, especially forming equipment, is corroded, so that theforming efficiency is lowered. Then, in the case where it is intended tosolve the corrosion problem of the forming equipment, other fining agentthan Cl, namely CeO₂ or SnO₂, may be used. However, such components tendto color the glass. In particular, CeO₂ is larger in an influence on thecoloration. Therefore, in the case where it is intended to prevent thecoloration of the glass, it is preferable to comprise SnO₂ in an amountof from 0.1 to 0.5% by mass without substantially comprising CeO₂. Byadopting such a constitution, for example, in the case of a transparentcrystallized glass in which a β-quartz solid solution precipitates, thetransmittance at 400 nm is liable to become 83% or more, and especially85% or more at the thickness of 1.1 mm.

A suitable composition range in the Li₂O—Al₂O₃—SiO₂ based crystallizedglass of the present invention is one comprising from 50 to 80% of SiO₂,from 12 to 30% of Al₂O₃, from 1 to 6% of Li₂O, from 0 to 5% of MgO, from0 to 10% of ZnO, from 0 to 8% of BaO, from 0 to 5% of Na₂O, from 0 to10% of K₂O, from 0 to 8% of TiO₂, from 0 to 7% of ZrO₂, and from 0 to 7%of P₂O₅, in terms of a percentage by mass. The reasons why thecomposition range is defined in this way are described below.Incidentally, the term “%” hereinafter means “% by mass” unlessotherwise indicated.

SiO₂ is a component of forming a skeleton of the glass and constitutinga crystal, and its content is from 50 to 80%, preferably from 52 to 77%,and more preferably from 54 to 75%. When the content of SiO₂ is toosmall, the coefficient of thermal expansion becomes excessively large,whereas when the content of SiO₂ is too large, melting of the glassbecomes difficult.

Al₂O₃ is a component of forming a skeleton of the glass and constitutinga crystal, and its content is from 12 to 30%, preferably from 13 to 28%,and more preferably from 14 to 26%. When the content of Al₂O₃ is toosmall, chemical durability is lowered, and the glass is liable todevitrify. On the other hand, when the content of Al₂O₃ is too large,the viscosity of the glass becomes too large, so that melting of theglass becomes difficult.

Li₂O is a crystal constituent component, and it gives a large influencein crystallinity and also works to lower the viscosity of the glass. Inaddition, Li is combined with chlorine in the melt to become relativelystable LiCl, which volatilizes to act as a fining gas. For that reason,in the Li₂O—Al₂O₃—SiO₂ based crystallized glass, even when Cl is usedsolely as the fining agent, by comprising a large amount of Li₂O, itbecomes possible to obtain a sufficient fining force. A content of Li₂Ois from 1 to 6%, preferably from 1.2 to 5.5%, and more preferably from1.4 to 5.0%. In particular, in the case where the fining agent is Clsolely without using an oxide fining agent such as SnO₂ and CeO₂, it ispreferable that the content Li₂O is 3% or more. When the content of Li₂Ois too small, the crystallinity of the glass is so weak that thecoefficient of thermal expansion becomes too large. In addition, in thecase of a transparent crystallized glass, a crystal is liable to yield awhite turbidity, and in the case of a white crystallized glass, alowering of whiteness is liable to occur. In addition to this, finingwith Cl solely becomes difficult. On the other hand, when the content ofLi₂O is too large, the crystallinity is too strong, so that the glassdevitrifies, or a metastable β-quartz solid solution is not obtained,and a crystal yields a white turbidity. Thus, it may be impossible toobtain a transparent crystallized glass. Incidentally, in the case ofusing SnO₂, 2.5% or more is preferable.

A content of MgO is from 0 to 5%, preferably 0 to 4.5%, and morepreferably from 0 to 4%. When the content of MgO is too large, thecrystallinity becomes strong, and the amount of a precipitated crystalincreases, so that the coloration by impurities becomes too strong.

A content of ZnO is from 0 to 10%, preferably 0 to 8%, more preferablyfrom 0 to 6%, and still more preferably from 0 to 5%. When the contentof ZnO is too large, the crystallinity becomes strong, and the amount ofa precipitated crystal increases, so that the coloration by impuritiesbecomes too strong.

In addition, the content of MgO and ZnO is preferably from 0 to 10%,more preferably from 0 to 8%, and even more preferably from 0 to 6% interms of a combined content (total amount). When the combined content ofthese components is too large, the coloration of the crystal is liableto become strong.

A content of BaO is from 0 to 8%, preferably from 0.3 to 7%, and morepreferably from 0.5 to 6%. When the content of BaO is too large,crystallization of a crystal is impaired, so that a sufficient crystalamount is not obtained, and the coefficient of thermal expansion becomestoo large. Furthermore, in the case of obtaining a transparentcrystallized glass, the crystal is liable to yield a white turbidity.

A content of Na₂O is from 0 to 5%, preferably from 0 to 4%, and morepreferably from 0 to 0.35%. When the content of Na₂O is too large, thecrystallinity becomes weak, so that a sufficient crystal amount is notobtained, and the coefficient of thermal expansion becomes too large.Furthermore, in the case of obtaining a transparent crystallized glass,the crystal is liable to yield a white turbidity.

A content of 1(₂0 is from 0 to 10%, preferably from 0 to 8%, morepreferably from 0 to 6%, and still more preferably from 0 to 5%. Whenthe content of K₂O is too large, the crystallinity becomes weak, so thata sufficient crystal amount can not be obtained, and the coefficient ofthermal expansion becomes too large. Furthermore, in the case ofobtaining a transparent crystallized glass, the crystal is liable toyield a white turbidity.

In addition, the content of Na₂O and K₂O is preferably from 0 to 12%,more preferably from 0 to 10%, and even more preferably from 0 to 8% interms of a combined content (total amount). When the combined content ofthese components is too large, the coefficient of thermal expansion isliable to become large. Furthermore, in the case of obtaining atransparent crystallized glass, the crystal is liable to yield a whiteturbidity.

TiO₂ is a nucleation agent, and its content is from 0 to 8%, preferablyfrom 0.3 to 7%, and more preferably from 0.5 to 6%. In particular, inthe case of comprising SnO₂, it is preferable that from 1.5 to 3%, from1.6 to 2.5%, and especially from 1.7 to 2.3%. When the content of TiO₂is too large, the coloration by impurities becomes remarkable.

ZrO₂ is a nucleation agent, and its content is from 0 to 7%, preferablyfrom 0.5 to 6%, and more preferably from 1 to 5%. When the content ofZrO₂ is too large, not only melting of the glass becomes difficult, butdevitrification tendency of the glass becomes strong.

In addition, in the case of comprising SnO₂, a combined content of TiO₂and ZrO₂ is preferably from 3.8 to 5%.

P₂O₅ is a component for enhancing the crystallinity of the glass, andits content is from 0 to 7%, preferably from 0 to 6%, and morepreferably from 0 to 5%. When the content of P₂O₅ is too large, thecoefficient of thermal expansion becomes too large. In addition, in thecase of obtaining a transparent crystallized glass, the crystal isliable to yield a white turbidity.

In the Li₂O—Al₂O₃—SiO₂ based crystallized glass of the presentinvention, it is possible to add various components other than theforegoing components. For example, each of SrO and CaO may be comprisedin an amount of up to 5%, and B₂O₃ may be comprised in an amount of upto 10%. In addition, for example, V₂O₅ can be comprised as a colorant inan amount of up to 1.5%, preferably up to 1.0%, and more preferably upto 0.8%. Incidentally, in the case of comprising SnO₂, SrO and CaOsatisfy a range of SrO+1.847CaO of preferably not more than 0.5, morepreferably not more than 0.4, and especially preferably not more than0.2. When the SrO+1.847CaO exceeds 0.5, a degree of coloration of thecrystallized glass becomes large, and white turbidity is liable togenerate.

Incidentally, in the present invention, as already described, for thereason from the environmental standpoint, it is important that As₂O₃ andSb₂O₃ are not substantially comprised. Cl, CeO₂, and SnO₂ may be used asa substitute fining agent for them. Here, a combination of the finingagents may be properly selected depending upon required characteristicsand the like. For example, in the case where the coloration of the glassis prevented from occurring, it is preferable to use Cl, or to use CeO₂and SnO₂ while strictly limiting their contents. In the case where it isintended to prevent corrosion of forming equipment or the like fromoccurring, it is preferable to use CeO_(2 or SnO) ₂. In the case whereit is intended to prevent both coloration of the glass and corrosion offorming equipment from occurring, it is preferable to comprise only SnO₂without using Cl and CeO₂.

Incidentally, according to investigations made by the present inventors,it has become clear that when the Al₂O₃ amount in a glass matrix phase(remaining glass phase) in the crystallized glass is large, thecoloration due to SnO₂ is reduced. In order to increase the Al₂O₃ amountin a glass matrix phase, it is effective to increase the Al₂O₃ amount ina mother glass composition. However, even when only the Al₂O₃ amount ina mother glass composition is simply increased, there is a tendency thata large proportion of Al₂O₃ as increased is distributed as a crystalconstituent component into a crystal phase, and the Al₂O₃ amount in aglass matrix phase hardly increases. Then, in the present invention, inthe case of using SnO₂, it is desirable to increase Al₂O₃ andsimultaneously to define Li₂O, MgO, and ZnO to specified ranges. This isbecause Li₂O, MgO, and ZnO tend to become crystal constituent componentstogether with Al₂O₃, and by defining the contents of these components,the Al₂O₃ amount to be distributed into the crystal phase can bedecreased. Specifically, it is preferable to comprise from 20.5 to 30%of Al₂O₃ and from 0.1 to 0.5% of SnO₂ and to adjust Li₂O, MgO, and ZnOto a range of 3.7≦Li₂O+0.741MgO+0.367ZnO≦4.5 in terms of a mass ratio.By adopting this constitution, it is possible to increase the Al₂O₃amount in the glass matrix phase in the crystallized glass, therebyeffectively reducing the coloration due to SnO₂. Incidentally, thecoefficients of MgO and ZnO are those for reducing the content of eachof the components into a mole of Li₂O.

Incidentally, it is preferable that the content of Al₂O₃ is from 20.5 to30%, from 21 to 28%, and especially from 21.5 to 26%.

In the foregoing constitution, when the content of Al₂O₃ is smaller than20.5%, an effect of SnO₂ for reducing the strengthening of colorationdue to TiO₂ and Fe₂O₃ is hardly obtained. On the other hand, when thecontent of Al₂O₃ is too large, the viscosity of the glass becomes toolarge, so that melting of the glass becomes difficult.

In the foregoing constitution, it is preferable that the content of SnO₂is from 0.1 to 0.5%, from 0.1 to 0.4%, and especially from 0.1 to 0.3%.When the content of SnO₂ is less than 0.1%, the effect as the finingagent is hardly obtained. On the other hand, when the content of SnO₂exceeds 0.5%, the coloration becomes too strong, so that thecrystallized glass is liable to become yellowish. In addition,devitrification is liable to occur.

In the foregoing constitution, it is preferable that the Li₂O+0.741MgO+0.367ZnO satisfies the range of from 3.7 to 4.5, from 3.8 to 4.4,and especially from 3.8 to 4.2. When the Li₂O+0.741MgO+0.367ZnO exceeds4.5, the Al₂O₃ amount in the glass phase in the crystallized glassdecreases, so that the effect for suppressing coloration by Al₂O₃ ishardly obtained. On the other hand, when the Li₂O+0.741 MgO+0.367ZnO isless than 3.7, a grain diameter of a Li₂O—Al₂O₃—SiO₂ based crystal inthe crystallized glass becomes large, so that white turbidity is liableto generate. As a result, there is a concern that a transparent feelingof the crystallized glass is impaired.

Next, the method of the present invention for producing the foregoingLi₂O—Al₂O₃—SiO₂ based crystallized glass is described.

First of all, a glass raw material batch is prepared so as to have adesired composition. As a glass composition, a glass comprising from 50to 80% of SiO₂, from 12 to 30% of Al₂O₃, from 1 to 6% of Li₂O, from 0 to5% of MgO, from 0 to 10% of ZnO, from 0 to 8% of BaO, from 0 to 5% ofNa₂O, from 0 to 10% of K₂O, from 0 to 8% of TiO₂, from 0 to 7% of ZrO₂,and from 0 to 7% of P₂O₅ can be exemplified. The reasons for definitionand suitable ranges with respect to this glass composition range arethose as already described, and therefore, explanations thereof areomitted herein.

Furthermore, at least one of a chloride, a Ce compound, and a Sncompound is added as a fining agent to the glass raw material batch. Inthe case of adding a chloride, its addition amount is from 0.04 to 0.3%,preferably from 0.08 to 0.2%, and more preferably from 0.1 to 0.18% interms of Cl based on 100% by mass of the glass raw material batch. Inthe case of adding a Ce compound, as to its addition amount, a contentof from 0 to 0.2%, preferably from 0 to 0.15%, and more preferably from0 to 0.1% in terms of CeO₂ based on 100% by mass of the glass rawmaterial batch is added. In the case of adding a Sn compound, as to itsaddition amount, a content of from 0 to 0.5%, preferably from 0 to 0.3%,and more preferably from 0 to 0.2% in terms of SnO₂ based on 100% bymass of the glass raw material batch is added. Incidentally, as alreadydescribed, it is important that As₂O₃ and Sb₂O₃ are not added to theglass raw material. In addition, in an application in which thecoloration of the glass is strictly controlled, in the case of usingSnO₂ as a fining agent, it is preferable to prepare a glass so as tocomprise from 20.5 to 30% by mass of Al₂O₃ and from 0.1 to 0.5% by massof SnO₂ and to fall within a range of 3.7≦Li₂O+0.741MgO+0.367ZnO≦4.5.The reasons for definition and suitable ranges with respect to thisglass composition range are those as already described, and therefore,explanations thereof are omitted herein.

In order that the S amount in the thus obtained glass may not be morethan 10 ppm in terms of SO₃, the amount of S which is incorporated as animpurity in the raw material is controlled to not more than 150 ppm,preferably not more than 100 ppm, and more preferably not more than 60ppm in terms of SO₃. In order to decrease the S content in the rawmaterial, a glass raw material with high purity is selected. Measuressuch as a selection of a grass raw material with high purity or apre-treatment of the glass raw material may be adopted.

Subsequently, the glass raw material is melted by melting furnace,especially a tank furnace capable of achieving continuous production. Inthe case of a glass of the foregoing composition, it is preferable thata melting condition is at a maximum temperature of from 1,600 to 1,800°C. for from about 20 to 200 hours.

Subsequently, the glass melt is formed into a desired shape to obtain aLi₂O—Al₂O₃—SiO₂ based crystallizable glass. As a forming method, variousmethods such as roll forming, press forming, and float forming can beadopted. The “crystallizable glass” as referred to herein means a glassbeing an amorphous state and having such properties that when heattreated, it precipitates a crystal from a glass matrix to become acrystallized glass.

Subsequently, a formed body consisting of a Li₂O—Al₂O₃—SiO₂ basedcrystallizable glass is held at from 700 to 800° C. for from 1 to 4hours to achieve nucleation. In the case of obtaining a transparentcrystallized glass, a heat treatment is carried out at from 800 to 950°C. for from 0.5 to 3 hours, thereby precipitating a β-quartz solidsolution. In addition, in the case of obtaining a white opaquecrystallized glass, after the nucleation, a heat treatment may becarried out at from 1,050 to 1,250° C. for from 0.5 to 2 hours, therebyprecipitating a β-spodumene solid solution.

In this way, it is possible to obtain a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass which does not substantially comprise As₂O₃ andSb₂O₃. Incidentally, the obtained Li₂O—Al₂O₃—SiO₂ based crystallizedglass is provided for various applications after being subjected to postprocessing such as cutting, polishing, bending processing and drawingforming, or being subjected to decoration on the surface.

Incidentally, as a measure for more decreasing the S amount in thecrystallized glass, there may be adopted methods such as (1) a method ofadding SnO₂, (2) a method of increasing a water content in the glassmelt in the presence of Cl, (3) a method of increasing a water contentin the glass melt in the presence of Cl adjusting a grain size of a SiO₂raw material, (4) a method of optimizing a batch melting temperature,and (5) a method of optimizing a melting efficiency. By properlycombining these methods, it becomes possible to obtain a crystallizedglass with a smaller S content. Each of these methods is hereunderdescribed in detail. (1) Method of adding SnO₂:

By adding SnO₂, it is possible to decrease the amount of dissolved SO₃in the glass. It may be considered that this is caused due to the factthat the S component in the glass melt is removed by a fining gasreleased from the fining agent component. In addition, SnO₂ hasproperties of releasing a fining gas at a higher temperature than thatin As₂O₃ or Sb₂O₃ and hardly releases oxygen at the initial stage ofmelting where the temperature is low. Namely, even if SnO₂ is added, theatmosphere at the initial stage of melting hardly becomes oxidative. Inview of the fact that when the atmosphere at the initial stage ofmelting becomes oxidative, S is easily dissolved into the glass melt, sothat the remaining S amount is liable to become large, it may beconsidered that if SnO₂ is used, it is possible to effectively suppressthe dissolution of S at the initial stage of melting. In the case ofadopting this method, an addition amount of SnO₂ is preferably not lessthan 0.1% by mass.

(2) Method of Adjusting a Water Content in the Glass Melt in thePresence of Cl:

According to investigations by the present inventors, different from asoda lime glass or the like having a high S solubility, in theLi₂O—Al₂O₃—SiO₂ based crystallized glass having a low S solubility, evenby simply increasing the water content, the S content in the glass meltcannot be decreased. However, when Cl is present in the glass melt, itis possible to remarkably decrease the S content. Though details of thismechanism are unclear, it may be considered that when water and Cl arecoexistent, a HCl gas is generated, and following the gas generation, Svolatilizes, so that the S content in the glass melt decreases. Thelarger the water content in the glass melt, the higher the effect fordecreasing the S amount is. In order to increase the water content inthe glass melt, there can be adopted methods such as a method of using araw material with a high water content, a method of increasing the watercontent in a combustion gas at the time of glass melting, and a methodof bubbling a water vapor in the molten glass. In addition, the watercontent of the glass melt can be expressed by a β-OH value of thecrystallized glass. In the present invention, the β-OH value of thecrystallized glass is preferably 0.2 /mm or more, more preferably from0.3 /mm to 4/mm, and even more preferably from 0.35 /mm to 4 /mm. In thecase where the crystallized glass is opaque, it is also possible tospecify it in terms of a β-OH value of the crystallizable glass. Asuitable β-OH value of the crystallizable glass is preferably 0.25 /mmor more, more preferably 0.30 /mm or more, and even more preferably0.36/mm or more.β-OH value (/mm)={log (T3850/T3500)}/t

T3850: Transmittance at 3850 cm⁻¹

T3500: Lowest transmittance in an absorption band in the vicinity of3500 cm⁻¹

t: Plate thickness of sample (mm)

(3) Method of Adjusting a Grain Size of a SiO₂ Raw Material

In the case of a glass with a low S solubility, such as aLi₂O—Al₂O₃—SiO₂ based crystallized glass, the S amount in the glass meltis influenced by a condition of initial melting at which the rawmaterial is melted. When a dissolution process of the raw material inthe Li₂O—Al₂O₃—SiO₂ based crystallized glass is analyzed, an initialmelt with a small SiO₂ component is first formed, into which the SiO₂raw material is then dissolved. Here, when the glass melt is reviewedfrom the point of view of acidity, since SiO₂ is a component having ahigh acidity, the acidity of the initial melt is low, and the acidityincreases with progress of the dissolution of the SiO₂ raw material. Inview of the fact that when the acidity of the glass is lower, S is moreeasily dissolved into the melt, it may be considered that when theacidity of the initial melt is lower, a glass melt comprising a lot of Sis liable to be formed. In other words, so far as SiO₂ is liable to bedissolved at the stage of initial dissolution of the raw material, S ishardly dissolved into the glass melt. As a result, reboil due to S ishardly generated. From these reasons, it is desirable to make a grainsize of the SiO₂ raw material small, thereby making it easy to dissolvethe SiO₂ raw material.

Specifically, as to the SiO₂ raw material, one having an average graindiameter of preferably not more than 180 μm, not more than 120 μm, andespecially not more than 100 μm is used. However, when the grain size ofthe SiO₂ raw material is too small, at the time of charging the rawmaterial, only the surface is rapidly melted by radiant heat, so thatthe S component in the inside is hardly volatilized and scattered.

As a result, there is brought a situation that the S amount of the glassmelt does not decrease. Then, it is preferable that a dissolution speedof the SiO₂ raw material does not become excessively high. Specifically,the average grain diameter of the SiO₂ raw material is preferably 45 μmor more, 50 μm or more, and especially 60 μm or more. The “average graindiameter” as referred to herein means as follows. That is, when sieveshaving various openings are used, proportions of grains passing throughthe sieves are measured, and a graph showing a relation between theopening and the proportion of grains passing through the sieve isprepared, a size of the opening of the sieve through which the grains inan amount corresponding to 50% pass is defined as the average graindiameter.

Incidentally, the method of adjusting the grain size of the SiO₂ rawmaterial can also be applied to other silica glasses.

(4) Method of Optimizing a Batch Melting Temperature:

It is desirable to set a batch melting temperature preferably at atemperature of log η=2.3 to 3.0, more preferably at a temperature of logη=2.3 to 2.9, and even more preferably at a temperature of log η=2.4 to2.9. Here, n is dPa·s. When the batch melting temperature is too high,the batch becomes in a state of being easily melted, and at the time ofcharging the raw material, only the surface is rapidly melted by radiantheat, so that the S component in the inside is hardly volatilized andscattered. On the other hand, when the batch melting temperature is toolow, since the SiO₂ raw material is hardly melted, an initial melt withlow acidity is formed, and the S content is liable to become high.Incidentally, the batch melting temperature can be determined bymeasuring a side wall in the vicinity of the glass raw material batchhaving been put in a glass melting furnace by using a radiationthermometer.

(5) Method of Optimizing a Melting Efficiency:

By prolonging the melting time, it becomes possible to remove unlinedbubbles in the glass melt. In addition, the S amount can be decreased.However, long-term melting lowers the productivity, and it is difficultto provide an inexpensive glass. In addition, when the melting time istoo long, a hetero layer is liable to be formed on the glass surface dueto volatilization. As already described, in a glass with low Ssolubility, S is easily gasified by a slight change of the state such asa composition change. Under these circumstances, it is desirable toappropriately control the melting time. As an index of the melting time,a melting efficiency (melting area/flow rate) can be adopted.Specifically, the melting efficiency is preferably from 1.0 to 5.0m²/(t/day), and especially preferably from 1.5 to 4.5 m²/(t/day).

EXAMPLES

The present invention is hereunder described by reference to thefollowing Examples.

Example 1

Table 1 shows examples of the present invention (Samples Nos. 2 to 6 and9 to 12) and comparative examples (Samples Nos. 1, 7, and 8).

TABLE 1 Sample No. 1 2 3 4 5 6 SiO₂ 66 65.8 65.6 66 66 68 Al₂O₃ 23 23 2323 23 23 Li₂O 4 4 4 4 4 2 MgO 1 1 1 1 1 1 BaO 1.5 1.5 1.5 1.5 1.5 1.5Na₂O 0.5 0.5 0.5 0.5 0.5 0.5 TiO₂ 2 2 2 2 2 2 ZrO₂ 2 2 2 2 2 2 Additionamount (% by mass) Cl — — — 0.16 0.08 0.16 SnO₂ — 0.2 — — — — CeO₂ — —0.4 — — — SO₃ in raw material 120 120 120 120 120 120 (ppm) Analyzedvalue (ppm) SO₃ 14 7 9 3 5 8 Cl <50 <50 <50 800 400 800 Analyzed value(% by mass) SnO₂ — 0.2 — — — — CeO₂ — — 0.4 — — — Reboil due to stirringGenerated Not Not Not Not Not generated generated generated generatedgenerated Number of bubbles 700 30 50 5 50 50 in product (/kg) β-OH(/mm) 0.5 0.5 0.5 0.5 0.5 0.5 Transmittance 85.5 80 75 85 85 <70 (%, at400 nm) (yield white turbidity) Sample No. 7 8 9 10 11 12 SiO₂ 65.8 6666.8 66.8 66.6 66.9 Al₂O₃ 23 23 23 23 23 23 Li₂O 4 4 3.5 3.5 3.5 3.5 MgO1 1 0.5 0.5 0.5 0.5 BaO 1.5 1.5 1.5 1.5 1.5 1.5 Na₂O 0.5 0.5 0.5 0.5 0.50.5 TiO₂ 2 2 2 2 2 2 ZrO₂ 2 2 2 2 2 2 Addition amount (% by mass) Cl0.16 0.25 — — — — SnO₂ 0.2 — 0.2 0.2 0.4 0.1 CeO₂ — — — — — — SO₃ in rawmaterial 300 300 120 50 80 120 (ppm) Analyzed value (ppm) SO₃ 11 11 6 32 9 Cl 800 1300 <50 <50 <50 <50 Analyzed value (% by mass) SnO₂ 0.2 —0.2 0.2 0.4 0.1 CeO₂ — — — — — — Reboil due to stirring GeneratedGenerated Not Not Not Not generated generated generated generated Numberof bubbles 250 250 30 5 1 60 in product (/kg) β-OH (/mm) 0.5 0.5 0.5 0.50.5 0.5 Transmittance 80 85 85 85 83 85.5 (%, at 400 nm)

Each of the samples was prepared in the following manner.

First of all, silica sand, alumina, lithium carbonate, barium nitrate,magnesium oxide, sodium nitrate, titanium oxide, zirconium oxide, andthe like were compounded so as to have a composition shown in Table 1(each of the numeral values shown in Table 1 means a mass percentage).Furthermore, NaCl, SnO₂, and CeO₂ were added in proportions shown inTable, followed by uniformly mixing. Thereafter, this raw material batchwas put into a refractory furnace (tank furnace for continuousproduction) by oxygen combustion and melted at a melting efficiency of2.5 m²/(t/day). Incidentally, the Cl amount “<50 ppm” of Samples Nos. 1to 3 and 9 to 12 in Table shows that the Cl amount comprised as animpurity is less than 50 ppm.

Subsequently, the glass melt was stirred with a platinum stirrer andthen roll formed in a thickness of 4 mm, followed by cooling to roomtemperature within an annealing furnace.

Thereafter, the crystallizable glass sample obtained by cutting into aprescribed length was analyzed with respect to SO₃ amount, Cl amount,SnO₂ amount, and CeO₂ amount in the glass. In addition, the presence orabsence of the generation of reboil due to stirring was evaluated. Theresults are shown in Table 1.

As is evident from Table, the examples of the present invention in whichthe amount of SO₃ comprised in the raw material is not more than 150ppm, or the SO₃ amount in the glass is not more than 10 ppm, the reboildue to stirring was not generated.

In addition, in the samples in which the SO₃ amount in the glass is lessthan 5 ppm, bubble in a product was distinctly few. In comparisonbetween Samples Nos. 4 and 6 and between Samples Nos. 10 and 12, in thesamples in the SO₃ amount in the glass is smaller, bubble in the productwas few. Though the reboil is generated chiefly at the time of stirring,besides, it is also generated even slightly at an interface with therefractory or the like. It may be considered that when the SO₃ amount inthe glass is small, this reboil generated even slightly can besuppressed. For that reason, it is understood that if the SO₃ amount inthe glass can be controlled to less than 5 ppm, a glass with higherquality can be obtained.

Incidentally, the SO₃ amount in the glass is a value determined bydipping an analysis sample in Na₂CO₃ by means of alkali fusion andfiltering with a filter paper, and subsequently stirring a filtratethereof with an ion exchange resin and again filtering, followed bymeasuring by means of ion chromatography.

The Cl amount, the SnO₂ amount, and the CeO₂ amount in the glass wereeach a value determined by subjecting a plate-shaped analysis sample tomirror polishing and measuring by a fluorescent X-ray analyzer.

The presence or absence of the generation of reboil due to stirring wasevaluated in the following manner. That is, a number of bubbles in eachof a glass collected before stirring with the platinum stirrer and aglass after forming was calculated into a number of bubbles per kg.Then, in the case where the number of bubbles in the glass after formingwas two times or more as compared with the number of bubbles in theglass before stirring, the reboil was evaluated to generate.

Bubble in the product is one obtained by irradiating light from a sideface of the plate-shaped sample, visually observing bubbles, andcalculating them into a number of bubbles per kg.

Subsequently, the crystallizable glass sample was put in an electricfurnace and subjected to a heat treatment according to the following twoschedules, respectively, thereby achieving crystallization, followed byfurnace cooling.

(1) Nucleation: 780° C. for 2 hours→Crystal growth: 900° C. for 3 hours

(2) Nucleation: 780° C. for 2 hours→Crystal growth: 1,160° C. for 1 hour

Incidentally, the rate of temperature rise from room temperature to thenucleation temperature was set to 300° C./h, and the rate of temperaturerise from the nucleation temperature to the crystal growth temperaturewas set to from 100 to 200° C./h.

Each of the obtained samples was evaluated with respect to the maincrystal and appearance. In addition, the transparent crystallized glasssample produced according to the schedule (1) was further measured withrespect to a β-OH value and a transmittance at 400 nm.

As a result, in all of the samples, when the heat treatment was carriedout according to the schedule (1), a transparent crystallized glass inwhich a β-quartz solid solution precipitated as a main crystal wasobtained. When the heat treatment was carried out according to theschedule (2), a white opaque crystallized glass in which a β-spodumenesolid solution precipitated as a main crystal was obtained.

In addition, in Samples Nos. 4 and 5, each of which did not compriseCeO₂ and comprised 3% or more of Li₂O, a high transmittance wasobtained. In addition, in Samples Nos. 9 to 12, as prepared in a rangeof 3.7≦Li₂O+0.741MgO+0.367ZnO)≦4.5, nonetheless SnO₂ was comprised, ahigh transmittance was obtained.

Incidentally, the main crystal was evaluated using an X-ray diffractionapparatus.

The appearance was visually observed.

The β-OH value was measured with respect to a mirror polishedplate-shaped sample in a thickness of 3 mm by using an infrared spectralphotometer (Perkin Elmer Spectrum GX).

The transmittance at 400 nm was measured with respect to a mirrorpolished plate-shaped sample in a thickness of 1.1 mm by using aspectral photometer (UV3100PC).

Example 2

Table 2 shows examples of the present invention in which a n-OH valuewas adjusted in the presence of Cl (Samples Nos. 16 and 17) andcomparative examples (Samples Nos. 13 to 15 and 18).

TABLE 2 Sample No. 13 14 15 16 17 18 Raw material (ppm) SO₃ 120 120 120120 120 300 Cl 80 800 1500 2000 2000 200 Glass (ppm) SO₃ 15 11 11 3 3 12Cl <50 400 800 800 800 100 Crystallized glass (/mm) β-OH value 0.10 0.100.10 0.30 0.40 0.30 Heating system Electric Electric Electric Oxygen &Oxygen & Oxygen & electric electric electric Melting efficiency 2.5 2.52.5 2.5 2.5 2.5 (m²/(t/day)) Reboil due to stirring Generated GeneratedGenerated Not Not Generated generated generated

Each of the samples was prepared in the following manner.

First of all, silica sand, alumina, lithium carbonate, barium nitrate,sodium nitrate, titanium oxide, zirconium oxide, and the like werecompounded so as to have a composition comprising 67% of SiO₂, 23% ofAl₂O₃, 4% of Li₂O, 1.5% of BaO, 0.5% of Na₂O, 2% of TiO₂, and 2% of ZrO₂in terms of a percentage by mass and to have a S amount shown in Table2. Furthermore, a chloride (NaCl, KCl, BaCl₂, and the like) was added ina chlorine proportion shown iohn Table 2, followed by uniformly mixing.Thereafter, this raw material batch was melted in a heating system andat a melting efficiency shown in Table 2. Incidentally, the Cl amount“<50 ppm” of Sample No. 13 in Table shows that the amount of Clcomprised as an impurity is less than 50 ppm. In addition, the term“electric” in Table means an electric melting system; the term “oxygen”means an oxygen combustion system; and the term describing the bothmeans a combination of the both systems. In addition, the SO₃ amount inthe raw material is a value determined by dipping an analysis sample inNa₂CO₃ by means of alkali fusion and filtering with a filter paper, andsubsequently stirring a filtrate thereof with an ion exchange resin andagain filtering, followed by measuring by means of ion chromatography.

Subsequently, the glass melt was stirred with a platinum stirrer andthen roll formed in a thickness of 4 mm, followed by cooling to roomtemperature within an annealing furnace.

Thereafter, the crystallizable glass sample obtained by cutting into aprescribed length was analyzed with respect to SO₃ amount and Cl amountin the glass. In addition, the presence or absence of the generation ofreboil due to stirring was evaluated.

Incidentally, the SO₃ amount in the glass is a value determined bydipping an analysis sample in Na₂CO₃ by means of alkali fusion andfiltering with a filter paper, and subsequently stirring a filtratethereof with an ion exchange resin and again filtering, followed bymeasuring by means of ion chromatography.

The Cl amount in the glass was a value determined by subjecting aplate-shaped analysis sample to mirror polishing and measuring by afluorescent X-ray analyzer.

The presence or absence of the generation of reboil due to stirring wasevaluated in the following manner. That is, a number of bubbles in eachof a glass collected before stirring with the platinum stirrer and aglass after forming was calculated into a number of bubbles per kg.Then, in the case where the number of bubbles in the glass after formingwas two times or more as compared with the number of bubbles in theglass collected before stirring, the reboil was evaluated to generate.

Subsequently, the crystallizable glass sample was put in an electricfurnace and subjected to a heat treatment according to a schedule ofperforming nucleation at 780° C. for 2 hours and crystal growth at 900°C. for 3 hours (schedule 1) thereby achieving crystallization, followedby furnace cooling. Each of the thus obtained samples was measured withrespect to the β-OH value. In addition, each of the obtained samples wasmeasured with respect to the main crystal and appearance.

As a result, in all of the samples, a transparent crystallized glass inwhich a β-quartz solid solution precipitated as a main crystal wasobtained. Furthermore, as is evident from Table 2, in Samples Nos. 16and 17 in which the β-OH value or the S amount in the raw material wasadjusted in such a manner that the S amount of the glass was not morethan 10 ppm, the reboil was not generated. Incidentally, instead of theschedule 1, the heat treatment was carried out according to a scheduleof performing nucleation at 780 ° C. for 2 hours and crystal growth at1,160 ° C. for 1 hour (schedule 2). As a result, a white opaquecrystallized glass in which a β-spodumene solid solution precipitated asa main crystal was obtained.

Incidentally, the β-OH value was measured with respect to a mirrorpolished plate-shaped sample in a thickness of 3 mm by using an infraredspectral photometer (Perkin Elmer Spectrum GX).

The main crystal was evaluated using an X-ray diffraction apparatus.

The appearance was visually observed.

In all of Schedules 1 and 2, the rate of temperature rise from roomtemperature to the nucleation temperature was set to 300° C./h, and therate of temperature rise from the nucleation temperature to the crystalgrowth temperature was set to from 100 to 200° C./h.

Example 3

The present invention is hereunder described by reference to thefollowing examples and comparative example.

Table 3 shows examples of the present invention (Samples Nos. 20 and 21)and a comparative example (Sample No. 19).

TABLE 3 Sample No. 19 20 21 SO₃ in raw material (ppm) 120 120 120 Grainsize of SiO₂ raw 10 60 90 material (μm) SO₃ in glass (ppm) 16 9 7 ReboilGenerated Not generated Not generated

Each of the samples was prepared in the following manner.

First of all, silica sand, alumina, lithium carbonate, barium nitrate,sodium nitrate, titanium oxide, zirconium oxide, and the like werecompounded so as to have a composition comprising 67% of SiO₂, 23% ofAl₂O₃, 4% of Li₂O, 1.5% of BaO, 0.5% of Na₂O, 2% of TiO₂, and 2% of ZrO₂in terms of a percentage by mass. Furthermore, NaCl was comprised in aproportion of 0.2% by mass as Cl, followed by uniformly mixing. At thattime, each of raw materials having an average particle diameter shown inTable was used as the SiO₂ raw material.

Subsequently, this raw material batch was put into a refractory furnace(tank furnace for continuous production) by oxygen combustion and meltedat a melting efficiency of 2.5 m²/(t/day). Subsequently, the glass meltwas stirred with a platinum stirrer and then roll formed in a thicknessof 4 mm, followed by cooling to room temperature within an annealingfurnace.

Thereafter, the crystallizable glass sample obtained by cutting into aprescribed length and measured with respect to the presence or absenceof the generation of reboil. The results are shown in Table 3.

As is evident from Table, in Nos. 20 and 21, the reboil due to stirringwas not generated.

Incidentally, the SO₃ amount in each of the raw material and the glassis a value determined by dipping an analysis sample in Na₂CO₃ by meansof alkali fusion and filtering with a filter paper, and subsequentlystirring a filtrate thereof with an ion exchange resin and againfiltering, followed by measuring by means of ion chromatography.

The presence or absence of the generation of reboil was decided in thefollowing manner. That is, a number of bubbles in each of a glasscollected before stirring with the platinum stirrer and a glass afterforming was calculated into a number of bubbles per kg. Then, in thecase where the number of bubbles in the glass after forming was twotimes or more as compared with the number of bubbles in the glass beforestirring, the reboil was evaluated to generate.

Subsequently, the crystallizable glass sample was put in an electricfurnace and subjected to a heat treatment according to the following twoschedules, respectively, thereby achieving crystallization, followed byfurnace cooling.

(1) Nucleation: 780° C. for 2 hours→Crystal growth: 900° C. for 3 hours

(2) Nucleation: 780° C. for 2 hours→Crystal growth: 1,160° C. for 1 hour

Incidentally, the rate of temperature rise from room temperature to thenucleation temperature was set to 300° C./h, and the rate of temperaturerise from the nucleation temperature to the crystal growth temperaturewas set to from 100 to 200° C./h.

Each of the obtained samples was evaluated with respect to the maincrystal and appearance. As a result, in all of the samples, when theheat treatment was carried out according to the schedule (1), atransparent crystallized glass in which a β-quartz solid solutionprecipitated as a main crystal was obtained. When the heat treatment wascarried out according to the schedule (2), a white opaque crystallizedglass in which a β-spodumene solid solution precipitated as a maincrystal was obtained.

Incidentally, the main crystal was evaluated using an X-ray diffractionapparatus.

The appearance was visually observed.

While the present invention has been described in detail and withreference to specific embodiments thereof, it will be apparent to oneskilled in the art that various changes and modifications can be madetherein without departing from the spirit and scope of the presentinvention.

Incidentally, the present application is based on a Japanese patentapplication filed on May 31, 2010 (Japanese Patent Application No.2010-123764), a Japanese patent application filed on Jul. 12, 2010(Japanese Patent Application No. 2010-157655), and a Japanese patentapplication filed on Jul. 22, 2010 (Japanese Patent Application No.2010-164450), the contents of which are incorporated herein byreference. In addition, all references as cited herein are incorporatedas a whole.

INDUSTRIAL APPLICABILITY

The Li₂O—Al₂O₃—SiO₂ based crystallized glass of the present inventioncan be utilized for various applications. Specifically, there can beexemplified front windows of oil stoves, wood stoves, and the like,substrates for high-technology products such as color filter substrates,image sensor substrates, substrates for top plates of electromagneticcookers, gas cookers, and the like, window glasses for fire-retardingdoors, base materials for reflecting mirrors to be used for projectorssuch as liquid crystal projectors, or light source lamps forillumination, setters for heat treatment of electronic components orplasma display panels, trays for microwave ovens, and electroniccomponents or precision machine components.

The invention claimed is:
 1. A method for producing a Li₂O—Al₂O₃—SiO₂based crystallized glass not substantially comprising As₂O₃ and Sb₂O₃,the method comprising: (i) preparing a glass raw material compounded soas to form a glass comprising Li₂O, Al₂O₃, and SiO₂, as a glasscomposition; (ii) melting the glass raw material in a tank furnace toobtain a glass melt; (iii) forming the glass melt into a Li₂O—Al₂O₃—SiO₂based crystallized glass; (iv) heat treating the crystallized glass toobtain a Li₂O—Al₂O₃—SiO₂ based crystallized glass in which a β-quartzsolid solution and/or a β-spodumene solid solution as a main crystal,said Li₂O—Al₂O₃—SiO₂, based crystallized glass comprising: (a) not morethan 100 ppm As₂O₃ and not more than 100 ppm Sb₂O₃ ; and (b) at leastone of: 50 to 1500 ppm Cl, not more than 200 ppm CeO₂, and 0.1 to 0.5%by mass SnO₂, wherein selection of the glass raw material and adjustmentof a production condition are performed so that the crystallized glasshas (c) a S content of 2 to 10 ppm in terms of SO₃and (d) a β-OH valueof 0.2 /mm or more.
 2. A method for producing a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass not substantially comprising As₂O₃ and Sb₂O₃, themethod comprising: (i) preparing a glass raw material compounded so asto form a glass comprising Li₂O, Al₂O₃, and SiO₂ as a glass compositionand limiting a content of S to 50 to 150 ppm, in terms of SO₃, andfurther comprising at least one of: (a) a chloride in an amount of from0.04 to 0.3% by mass in terms of Cl based on 100% by mass of the glassraw material; (b) a Ce compound in an amount of from 0 to 0.2% by massin terms of CeO₂ based on 100% by mass of the glass raw material; and(c) a Sn compound in an amount of from 0.1 to 0.5% by mass in terms ofSnO₂ based on 100% by mass of the glass raw material; (ii) melting theglass raw material in a tank furnace to obtain a glass melt; (iii)forming the glass melt into a Li₂O—Al₂O₃—SiO₂ based crystallized glass;(iv) heat treating the crystallized glass to obtain a Li₂O—Al₂O₃—SiO₂based crystallized glass in which a β-quartz solid solution and/or aβ-spodumene solid solution as a main crystal, said crystallized glasscomprising no more than 100 ppm As₂O₃; and no more than 100 ppm Sb₂O₃;wherein selection of the glass raw material and adjustment of aproduction condition are performed so that the crystallized glass has aβ-OH value of 0.2 /mm or more.
 3. The method for producing aLi₂O—Al₂O₃—SiO₂ based crystallized glass according to claim 1 or 2,wherein the glass raw material comprises the chloride in an amount offrom 0.04 to 0.3% by mass in terms of Cl based on 100% by mass of theglass raw material.
 4. The method for producing a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass according to claim 1 or 2, wherein the glass rawmaterial comprises SnO₂ in an amount of from 0.1 to 0.5% by mass, and noCe compound is added.
 5. The method for producing a Li₂O—Al₂O₃—SiO₂based crystallized glass according to claim 1, wherein the glass rawmaterial is compounded so as to form a glass comprising from 50 to 80%of SiO₂, from 12 to 30% of Al₂O₃, from 1 to 6% of Li₂O, from 0 to 5% ofMgO, from 0 to 10% of ZnO, from 0 to 8% of BaO, from 0 to 5% of Na₂O,from 0 to 10% of K₂O, from 0 to 8% of TiO₂, from 0 to 7% of Zr0 ₂, andfrom 0 to 7% of P₂O₅, in terms of a percentage by mass.
 6. The methodfor producing a Li₂O—Al₂O₃—SiO₂ based crystallized glass according toclaim 1 or 2, wherein the glass raw material is compounded so as to forma glass comprising from 20.5 to 30% by mass of Al₂O₃ and from 0.1 to0.5% by mass of SnO₂ and satisfying a relation of3.7≦Li₂O+0.741MgO+0.367ZnO≦4.5 in terms of a mass ratio.
 7. The methodfor producing a Li₂O—Al₂O₃—SiO₂ based crystallized glass according toclaim 1, wherein the glass raw material comprises a chloride, and acontent of S of 50 to 150 ppm in terms of SO₃.
 8. The method forproducing a Li₂O—Al₂O₃—SiO₂ based crystallized glass according to claim7, wherein the glass raw material comprises chloride in an amount offrom 0.01 to 0.3% by mass in terms of Cl based on 100% by mass of theglass raw material.
 9. The method for producing a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass according to claim 7, wherein the glass raw materialfurther comprises a Sn compound in an amount of not more than 0.5% bymass in terms of SnO₂, and no Ce compound is added.
 10. The method forproducing a Li₂O—Al₂O₃—SiO₂ based crystallized glass according to claim7, wherein the glass raw material is compounded so as to form a glasscomprising from 50 to 80% of SiO₂, from 12 to 30% of Al₂O₃, from 1 to 6%of Li₂O, from 0 to 5% of MgO, from 0 to 10% of ZnO, from 0 to 8% of BaO,from 0 to 5% of Na₂O, from 0 to 10% of K₂O, from 0 to 8% of TiO₂, from 0to 7% of ZrO₂, and from 0 to 7% of P₂O₅, in terms of a percentage bymass.
 11. The method for producing a Li₂O—Al₂O₃—SiO₂ based crystallizedglass according to claim 1 or 2, wherein melting the glass raw materialis performed with a melting efficiency (melting area/ flow rate) of 1.0to 5.0 m²/(t/day) in the tank furnace.
 12. The method for producing aLi₂O—Al₂O₃—SiO₂ based crystallized glass according to claim 1 or 2,wherein the glass raw material is compounded so as to form a glasscomprising from 20.5 to 30% of Al₂O₃, from 1.6 to 2.5% of TiO₂, and from0.1 to 0.5% by mass of SnO₂, and satisfying a relation of 3.7≦Li₂O+0.741MgO+0.367ZnO≦4.5 in terms of a mass ratio.
 13. The method for producinga Li₂O—Al₂O₃—SiO₂ based crystallized glass according to claim 2, whereinthe glass raw material is compounded so as to form a glass comprisingfrom 50 to 80% of SiO₂, from 12 to 30% of Al₂O₃, from 1 to 6% of Li₂O,from 0 to 5% of MgO, from 0 to 10% of ZnO, from 0 to 8% of BaO, from 0to 5% of Na₂O, from 0 to 10% of K₂O, from 0 to 8% of TiO₂, from 0 to 7%of ZrO₂, and from 0 to 7% of P₂O₅, in terms of a percentage by mass. 14.The method for producing a Li₂O—Al₂O₃—SiO₂ based crystallized glassaccording to claim 2 or 13, wherein the glass raw material is compoundedso as to form a glass comprising from 20.5 to 30% of Al₂O₃, from 1.6 to2.5% of TiO₂, and from 0.1 to 0.5% by mass of SnO₂, and satisfying arelation of 3.7≦Li₂O+0.741MgO+0.367ZnO≦4.5 in terms of a mass ratio. 15.A method for producing a Li₂O—Al₂O₃—SiO₂ based crystallized glass notsubstantially comprising As₂O₃ and Sb₂O₃, the method comprising: (i)preparing a glass raw material compounded so as to form a glasscomprising Li₂O, Al₂O₃, and SiO₂ as a glass composition and limiting acontent of S to 50 to 150 ppm in terms of SO₃; (ii) melting the glassraw material in a tank furnace to obtain a glass melt; (iii) forming theglass melt into a Li₂O—Al₂O₃—SiO₂ based crystallized glass; (iv) heattreating the crystallized glass to obtain a Li₂O—Al₂O₃—SiO₂ basedcrystallized glass in which a β-quartz solid solution and/or aβ-spodumene solid solution as a main crystal, said Li₂O—Al₂O₃—SiO₂ basedcrystallized glass comprising: (a) not more than 100 ppm As₂O₃ and notmore than 100 ppm Sb₂O₃; and (b) at least one of: 50 to 1500 ppm Cl, notmore than 200 ppm CeO₂, and 0.1 to 0.5% by mass SnO₂, wherein selectionof the glass raw material and adjustment of a production condition areperformed so that the crystallized glass has (c) a S content of 2 to 10ppm in terms of SO₃ and (d) a β-OH value of 0.2 /mm or more.
 16. Themethod for producing a Li₂O—Al₂O₃—SiO₂ based crystallized glassaccording to claim 15, wherein the glass raw material is compounded soas to form a glass comprising from 50 to 80% of SiO₂, from 12 to 30% ofAl₂O₃, from 1 to 6% of Li₂O, from 0 to 5% of MgO, from 0 to 10% of ZnO,from 0 to 8% of BaO, from 0 to 5% of Na₂O, from 0 to 10% of 1K₂O, from 0to 8% of TiO₂, from 0 to 7% of ZrO₂, and from 0 to 7% of P₂O₅, in termsof a percentage by mass.
 17. The method for producing a Li₂O—Al₂O₃—SiO₂based crystallized glass according to claim 15 or 16, wherein the glassraw material is compounded so as to form a glass comprising from 20.5 to30% of Al₂O₃, and from 0.1 to 0.5% by mass of SnO₂, and satisfying arelation of 3.7≦Li₂O+0.741MgO+0.367ZnO≦4.5 in terms of a mass ratio. 18.The method for producing a Li₂O—Al₂O₃—SiO₂ based crystallized glassaccording to claim 15 or 16, wherein the glass raw material iscompounded so as to form a glass comprising from 20.5 to 30% of Al₂O₃,from 1.6 to 2.5% of TiO₂, and from 0.1 to 0.5% by mass of SnO₂, andsatisfying a relation of 3.7≦Li₂O+0.741MgO+0.367ZnO≦4.5 in terms of amass ratio.